Catalysis



. having distillate Patented is, 1945 UNITED. STATES PATENT pm;

Hold" 7 a com of No Drawlnl.

I John I. Process Application Serial'No. 410,165 m Swarthmore. 7a., assignmto corporatlomwllmingtomllelc I Delaware 1 September 9, 1941,

The present invention relates to the conversion of hydrocarbons, ror example, hydrocarbon fractions obtained or derived from petroleum or other hydrocarbonaceous or carbonaceous materials in the presence of specific catalysts. One of its speciflc applications is the use of the catalysts in the production of valuable hydrocarbon products characteristics including stable; high anti-knock or in motor fuels.

The catalysts are synthetically prepared posltes containing ica, alumina and zirconia ation. They are further by high activity in drocarbons or fractions boiling within the boiling range of gasoline, by selectively promoting formation of stable products of high anti-knock value, by their tendency to form comparatively small quantities, of heavy undistillable products which accumulate as catalyst deposits, by their ability to maintain their catalytic properties for long periods under severe conditions of use including a multiplicity of regenerations by coinbustion to remove buroable deposit.

According to a specific and preferred embodi merit of the invention, ordinarily liquid hydrocarbons, for example, a distillate fraction having comin intimate associcomponents boiling within and/or above the boil;

ing range of gasoline, are subjected to conditions promoting splitting reactions, for example, conditions suitable for dehydrogenation and/or cracking, in the presence of such composites prepared by calculation of intimately associated silica, alumina and hydrous zirconia. To obtain tc fullest advantage activity, selectivity and refractory character of the composites'they should be free or substantially so of alkali metal utilized in the production or the silica and/or either or both of the, other precipitated oxides.

In practice of certain aspects of the invention, distillable hydrocarbon fractions, for example,

ordinarily liquid fractions such as low'anti-knock,

heavy or light naphtha, or alight or heavy gas oil, or a long residuum or topped petroleum crude may be processed at reforming or cracking temperature and at pressure suitable for maintaining the material in vapor phase during contact with the catalyst. Long catalyst liie and higher yields of liquid'products are usually obtained by utilization of composites comprising a major proportion of silica and minor proportions'of alumina'and of zirconia. The calcined composite should contain, however, a substantial quantity of alumina, usually at least 2% try-weight and fractions'valuable for use as precipitated or coagulated sll-"' ofabout by weight, as for characterized in part promoting formation of hyeither or both of the preferably above 3% by weight. when the alumina content exceeds about 40%, the catalyst, although still H g substantial and even high activity, sometimes produces lower yields of high anti-knock products than when lower quantitles of alumina are employed. To obtain the benefits of the process it is not necessary that the composite comprise large proportionate quantitles of zirconia. In fact, the desired catalytic properties are emphasized in composites containing this material in amounts not in excess example, from v 0.5% to about 15%. For mostordinarily liquid or vaporizable charging stocks, it is preferred to employ catalyst containing at least 4 mols and preferably at least 10 mols of silica for 'each mol of zirconia and each mol of alumina (10:1:1), as up to 01- mols of silica for each mol of other oxides. The composites of silica, alumina and hydrous zirconia may be prepared by a number of alternative methods characterized by common features which'tend to develop the properties desired in the finished contact mass.

According to one method, hydrous zirconia be deposited on or composited with hydrous eilica'and hydrous alumina. One way of doing this is to produce the three oxides from the same aqueous menstruum as by interaction in solution of an alkali metal silicate, an aluminum compound, and a zirconium compound, to produce a hydrous composite which upon drying,

. with or without preliminary washing to freedom from water soluble reaction products, isa zeolite containing silica, alumina, and zirconia as nuclear components and exchangeablyholding alkali metal. Another method is to deposit hydrous zirconia on composited silica and alumina prepared, for example, by coprecipitation or coagulation of silica and alumina or by compositing separately prepared hydrogels of gelatinous precipitants of silica-andalumina.

According to the latter method, the deposition may be eflected by mixing silica-alumina composites in hydrous or commiiiuted dried'condition with precipitated hydrous zirconia or by I treatment of such a composite of silica and alumina with a solution of a zirconium compound I will deposit orvmay be treated to deposit precipitated i vdrous zirconia. For example, the

hydrous or dried silica-alumina may be impregnated or mixed with a solution of a hydrolyzable salt of zirconium as, for example, zirconium sulphate, zirconium nitrate-zirconium oxychlorlde, etc.,-and then, it necessary. subjected to heat materials by reaction involving the which red ce solution. In the practice of this method, better results are obtained when the composite of silica and alumina, as presented for deposition of hydrous zirconia thereon, is a zeolite. At the time of deposition of hydrous zirconia, thereon,

the zeolite may exchangeably hold alkali metal or it may have been freed of alkali metal as, for

example, after the manner hereinafter described.

Another method is to composite separately Prepared hydrous silica, hydrous alumina and hydrous zirconia. The hydrous materials may be combined after being washed to freedom from soluble compounds thus producing directly a composite which is free of alkali metal. It is preferred, however, that the hydrous oxides be so combined that the resulting composite has the structure and other characteristics of a zeolite. One method of thus producing a zeolite is to present silica hydrogel to the compositing step in substantially its original'hydrous condition, that is. without intervening washing. Alternatively or additionally, hydrous alumina and/or hydrous airconia containing alkali metal oxide and resulting from the production of either or useof alkali metal compounds. such. for example, as an alkali metal aluminate or a precipitant comprising an alkalimetal cation, may be presented to the comp ifl ls step.

In each of the foregoing methods the composite, as prepared. contains zirconia in hydrous state. Another feature of great importance is that the composited silica, alumina and zirconia, as presented to the hydrocarbon treatment, should be free or substantially so of alkali metal.

7 To develop fully the activity and other desired characteristics of catalyst. it should contain no more alkali metal than that chemically equivalent to 0.5% by weight of sodium oxide, and for best resultsshould contain less than three-fifths of this amount. When the precipitatedoxides. at the time .or their combinationrare substanalkali metal. is driven out of metal removal consists of a base preferably'employing as base exchanging medium a solution of a compound ofa volatile orheat unstable cation which. aftersubstitution for the subsequent calcination to leave a finished catalyst composed of the substantially pure nucleus of the zeolite. thus be used amines, chloride.

, times results in an improved product. but 'acid both of these .of 11 or below tially tre of alkali metal it obviously follows that the composited materialsare also free of alkali metal. Such is the for example, when silica 'hydrogel' washed free of alkali metal is composited with hydrous alumina and hydrous zirconia prepared in the absence of alkali metal or washed free of the same. ready for calcination without further treatment.

Certain oithe above-described methods. as has been described, result in zeolites whose nuclei are composed of or contain silica. alumina and zirconia. The zeolites yield superior catalysts. and, in order that their catalytic properties be fully developed, it is usually necessary to subject them to chemical purification to remove alkali metal. Thus, according to the preferred aspects of the invention. zeolites containing silica, alu-.

mina and zirconia are produced and thereafter subjected treatment with a chemical agent fiheir content of alkali metal to or sodium oxide or equivalent andprefsubstantially complete removal of oxide. The most satisfactory alkali below 0.5 erably' efl'ects alkali metal Such composites are or addition anion bearing treatment suiliciently drastic to efl'ect substantially complete'removal of alkali metal often adversely afl'ects the, activit refractoriness, or both, of the zeolitic nucleus. 0n the otherhand. a base exchange step such as that described above rarely, if ever, has any deleterious effect on the desired properties of the finished catalyst.

In order to insure substantially complete reat least 0.2 and preferably at least 0.5 the total alkali metal oxide content of the reactionmixture, as set forth, for example, in my eopending applications, Serial No. 170.648, flied October 23.

1937, and Serial No. 174,966. filed November 17.

1937, which have now been issued as United States Patents Nos. 2,283,172 and 2,283,173. Quantities of anion at least equivalent to the alkali metal of the solutions insures easy and substantially complete elimination of alkali metal from the zeolite. In many instances the alkali metal content of the zeolite is substantially completely removable by base excfl-hnge when the precipitation is eii'ected and completed at pH and preferably not in excess of about 10, as'within the range of 3 to 10. Accordinch. in practice of the invention involving catalyst produced by coprecipitation methods, the coprecipitation is eflected in the presence of such quantity of a suitable anion, for example. the chloride anion,

the sulphate anion, the acetate anion or the nitrate-anion.

The requisite quantity of nonamphoteric anion may be provided in its entirety by the compounds selected for interaction with the alkali metal silicate as, for example, by utilization of soluble aluminum salts and/ or zirconium salts, or it may be provided to the reaction mixture of a suitable or a salt. When salts are employed it is preferable that they be of a volatile or heat unstable cation. for example, of ammonium or an amine.

Thus, for example, silica-alumina-zirconia aeolites may be prepared by interaction of a soluble silicate and soluble aluminum and zirconium salts. When this type of reaction is employed.-

the desired'and valuable properties are more pronounced, when the quantity of salt, together with any additional anion bearing compound, is controlled to produce a coagulant or precipitant of pH not in excess of about 8 and preferably of 7 or less. Highly desirable catalyst may, however, be produced under conditions of greater alkalinity. One method often tending to produce alkaline reaction conditions is utilization of alkali metal aluminate as the source of alumina.

exchanging step.

the zeolite upon t least in part by inclusion within compound, for example, an acid 'lhenscsssaryquantityofanionthsnmustcoms sequentuseincontactwithhydrocarbonreactfromasourceegtr'sneoustothesilicateandaiuvantsordnring regenerationbycontroiiedcomminate solutions. It may beprovided in partby bastion. In most. cases it is better to employ zirconium salt solution. Often. however, in'procaleination temperatures of at least 800 F. and

' in my aforesaid Patent No. 2,283,173, by interacting the same with a solution of a compound I preferably 900 10 tory character of the- 1". or higher.

If desired, preparation of the zeolite may include mild acid treatment effected before the calcination step. ,Such treatment. which often beneficially aifects the selectivity and-refraccataiyst, should, for best results,'be conducted on the dried aeolite after removal of alkali 'metaL. Such treatment may effectively and advantageously be combined with [5 alumina seolite.

bearing the necessary anion. Such solution may contain zirconium: salt, or the latter may be separately added to the mixture before or after addition of the sol of a supplementary anion hearing compound. Excellent catalysts are derived from alkaline gels or gelatinous precipitates pro-. duced by interaction of such silica-alumina sols with a solution or solutions containing salt and a compound, preferably a salt of -a volatile or heat unstable cation, which compound reacts by metathesis with the alkali DCtiJ'OXidG content of the sol to produce a salt and and base. Thus. for example, the sol may be'reacted with a solution of zirconium salt and an ammonium or amino salt selected from the group. ammonium chloride, ammonium nitrate,- amdeposition of hydrous zirconia upon the silica- "I'o this end, the zeolite may be immersed in or otherwise contacted with a solution of a zirconium salt, many of which, including zirconium sulphate, zirconium oxychloride and zirconium nitrate are sufficiently acid to co effect the desired treatment. Alternatively, the

silica-alumina zeolite maybe immersed in other acid reacting or acidulated zirconium-bearin menstruum, as for example, a zirconia gel or sol containing a small quantity of free acid.

It is characteristic of the cataLvsts embraced within the scope of the-invention that they are exceptionally stable to heat, being capable of maintaining desired activity for long commercial life involving repeated and frequent regeneraso tions by combustion of burnable deposit. Over monium sulphate, ammonium acetate, and methylamine or ethylamine hydrochloride.

In practicing the aspects of the invention involving the production of hydrous composites having zeolitic properties, desired catalytic properties and catalyst eflciency are developed to fuller extent 'by drying the hydrous or gelatinous composite while it retains all or substantially all water and water soluble materials contained within the structure of the gelatinous composite at the time of its formation, i. e., before any washing or base exchange. step. The drying temperatures employed are moderate,

cess of about 400 l". Before the base exchange step is effected it'is preferred to wash the resulting dry, hard, seolite free or substantially so. of the contained water soluble materials such as siso of alkali metal may be subiected to caleination before contacting it with the hydrocarbon reactants. The caicination step preferabLv involves utilization of temperatures sufllciently high to drive of! any volatile or heat unstable cation which may be exchangeably held or absorbed in the zeolite and also to destroy or re-;

duce base exchange properties possessed by the composite up to this point, thereby to produce a catalyst composed solely of the nucleus of a zeoiite or of such a nucleus containing deposited zirconia. To eilect these results. temperatures at least as high as 700' I. should be employed and it is preferable to employ temperatures at least as asthose encountered during suband above these advantages, which directly provide improved and more economical plant operatlon, these catalysts, despite being highly active in'promoting splitting and kindred decomposisrtion reactions. possess highly selective activity which direct the course of decomposition reactions toward products possessing a high degree of stability and marked anti-detonating characterlstics. Motor fuels produced by their. use

s0 under decomposition conditions, even without further purification, characteristically have high resistance to oxidation and .other deteriorating influences encountered in storage and use, as measured, for example, by oxygen bomb induction periods, accelerated gum determinations,- invoiving, for example, temperatures not in excolor stability tests, etc. In fact, these motor fuels are unique among those resulting from splitting and other decomposition reactions in that they possess the peculiar type of stability required of modem aviation gasolines and ourkali metal salts and excessive free alkali metal oxrently indicated by standardized acid heat or bromine number determinations. Utilizing a wide variety of charging stocks ranging from crude distillation residues to naphthas having boiling range characteristics of gas and i tin eluding cracked and other naphthas of high acid heat, gasolines made according to the invention have acid heats of 60 F. and below and usually 40 F. or below.

The splitting reactions are preferably conducted in vapor phase. For most charging stocks catalyst temperatures within the range 0:!

700 to 1050 I". are suitable, temperatures withing the lower portions of the range, as up to 950? I". being usually employed for the transformatively low pressures,

tion of high boiling hydrocarbons, and temperstures within the upper portion of the range; or

000 1''. and higher, for kerosenes and other naphthas. It is preferable to employ comparaas from atmospheric up to 150 or 200 lbs. per sq. in. gauge. Pressures of about 30 lbs. per sq. in. gauge and up are of some advantage in transforming the more refractory naphthas and similar charging stocks,

but it is preferred to use pressures beiow about Exams: 1

; A hydrous composite containing silica, zir-- nia and alumina in the approximate molar ratio of 15:0.9:-1 was prepared as follows; About 22.5 kilograms of a solution of commercial sodium silicate having a specific gravity of about 1.4 and diluted with about 8 liters of water was mixed with approximately 3.5 liters of ammonium hydroxide solution having a. specific gravity of.0.9. To this mixture there was added a second solution made up of approximately 3.5 ki1o-, grams of-commercial aluminum sulfate dissolved in about 50 liters of water mixed with about 6.5 liters of a solution of about 2 kilograms of zirconium sulfate. Within a minut an all embracing gel having a pH value of about 5.7 set up. This gel was dried, washed and treated with an ammonium chloride solution until the total sodium oxide content was reduced to below 0.5%. This product was divided into two portions.

I One portion was heat treated at about 1050* F. for two hours and was utilized to promote gasoline formation from an East Texas gas oil of the following properties:

Engler distillation Int. 440 5 464 484 49a 510 40 522 50 534 60 550 "I0 5'72 90 646 95 704 Dry 724 a. P. I. gravity 36.0-10.3 Sulphur I 0.8 Pour F 351-. 5 Flash (open cup) F 220: 10 Fire F 2501- 5 S. U. vis./100 40: 3 Conradson carbon 0.03 Aniline point F 16512.5

This gas oil was fed in vapor form to'the catalyst ata rateof about 1.5:1 volumes of gas oil to each volume of catalyst per hour for an operating period of approximately 10 minutes while maintaining'the catalyst at about 785 F. The fractionated 400 F. end point gasoline obtained from the'reaction products was found to amount to approximately 52% by volume of the gas oil charge. Upon analysis, the coke-like deposit on the catalyst was found to be less than 1.9% by weight or approximately 13 grams per liter of catalyst and was removed within a 10-minute burning period conducted at maximum temperature of 1100 1''. Upon extensive use this catalyst maintained its ability to form high yields of gasoline product, but its tendency to rccumulate coky deposit decreased.

The other portion of this catalyst was Subjected to heat treatment at about 1400 F. for 2 hours. When used in a process for producing 400 I", end point. gasoline utilizing the same charging stock and substantially the same operating conditions as for the first portion of the catalyst, it wasfound that substantially the same quantity of gasoline product was obtained. The catalyst deposit, however. was found to be approximately 1% by weight or about 7 grams .per liter.

The gasoline recovered in both the above runs had octane ratings in excess of '76 (C. F. R. motor method). Each gasoline had an acid heat value below .60".,;F. along with low copper dish gums and long oxygen bomb induction periods.

A typical illustration of the effectiveness of this catalyst in promoting transformation of low octane naphthas into high octane product is as follows. A heavy naphtha having a boiling range of the order of 280to 450 F. and an octane rat- 'ing of about 35 and obtained from East Texas crude was fed tov the second portion of the catalyst at the rate of about 1.25:1 under pressure of the order of .50 lbs. per sq. in gauge for a runof 20 minutes duration during which the catalyst was maintained at about a temperature of 820 F. The 400 F. end point gasoline separated by fractionation and condensation from the vapors issuing from the reaction zone was found to be equivalent to about'60% by volume of the fresh charge. Upon analysis, this gasoline had an octane rating of about 70 and the color and stability characteristics which typically result from practice of the invention. The coky deposit on the-catalyst was of the order of 0.8% of its-weight or about 5.5 grams per liter. This deposit was easily removable in a 10 minute burning period.

EXAIPLI 2 .portion of zirconiau In each instance. the catalyst was obtained from a composite of hydrous silica, hydrous alumina and hydrous zirconia prepared by interaction of a stream of silica-alumina sol with streams of zirconium sulphate solution and ammonium sulphate solution mixed therewith in rapid succession under conditions of turbulent flow to produce an alkaline gelatinous composite which wasdried at temperature in the range of. to 220 F., the zeolite washed free of water soluble substances, and then base-exchanged with a solution of ammonium'sulphate until its total content of sodium oxide was reduced to below 0.3% by weight. Aftercalcination each composite was utilized to promote cracking of a heavy East Texas bottoms fraction having boiling range of 490 to 945 F. and A. P. I. gravity of 28.6 in recurring cycles of on-stream and. regeneration periods. During the on-stream periods which were of ten minutes duration the bottoms, in vaporized condition, at pressure of about 8 lbs. per square inch gauge, and mixed with about 15% of their weight of steam. were fed to the catalyst at the rate of about one volume of liquid bottoms per hour for each volume of catalyst while maintaining the latter at'temperature of about 850 F. During regeneration periods the coky catalyst deposit was removed by combustion at controlled temperature within the approximate range of 800 to 1100 F. The products which issued from the catalyst during the on-stream periods were fractionated into 410 endpoint IOU ' cate solution containing about 28.5

' about 10.3 r 19.8 parts oi (NHDQBOd dissolved and ZrOz and the charge oi a 410 1.

' together with 45.5% by first two compositea'the gether with about rich as mass containing ties of branched chain com- To prepare the first hydrous 85parrsbyweightoi commercialsodiumsili- NasO, after dilution with about as parts by weight of water, was mixedwith about 4.3 parte'by commercial sodium aluminate 27.5 parts by weight of commercial zirconium sulin about 29.4 partsofwatertoproduceagelhavingpfiof about 9.2- Alter drying, washing, changing, the zeolite hours at temperature mosphere or steam. posed essentially of about 81.5% $102, 8.3% A1202 containing of the order or when cracking the above about 48% by volume of and point gasoline having octane rating (C. F. R. research method) of about 91 or about 80 '(C. F. R. motor method) volume of a clean iuel having distillate characteristics. The coke deposit on the catalyst amounted only to about 3.7% and the rich gas to about'10.'7% by weight 01 about 1200 F. in an at- 0.25% No.10. yielded. described heavy bottoms.

of the charge.

To produce the second composite a silica-alumina sol prepared by mixing with about 185 parts of water about 121 parts and 6.25 parts respectively. 01 the same sodium silicate and sodium alumina-to as described for the first composite of .this example was reacted in the manner described with about 16.5 parts of the said commercial zirconium sulphate solution diluted with about 33 arts'oi water and approximately 28.2 parts of ammonium sulphate dissolved in about 40.6 parts of water. The resulting gel, having pH of about 9.5, after the drying, washing base exchange and calcination steps employed with the first catalyst of the serle8,'was subjected to test. This catalyst. consisting essentially of about 85% S102. 9.4% A120: and-5.3% Z102 (its content of Halo being about 0.28%) produced about 46% byvolume of gasoline 01 about 89 ootane (C. F. R. research method) or about 80 (C. E. B. motor method) with an approximately 01 distillate fuel oil or cracking stock. The coke roduced as catalyst deposit was only about 4% and the rich gas about 10.5% by weight 01 the charge. I I 1 The third compositeloi this series was a gel or about 9.6 pH prepared silica-alumina sol containin8about126partsand65partsoithesodium silicate and sodium aluminate described to- 192 parts of water. The zirconium sulphate solution contained about 37 arts 0! the described commercial solution and about 41 parts of water while the ammonium sulphate solution was made up of about 29 parts of this salt and about 42 parts 01- water. After drying, washing, base exchange step and calcination substantially as employed with the other two composites. this composite, 46.5% by volume of the charge 01 gasoline-oi composite about 7 slot and 9% parts by weight of water and about- The resulting catalyst, comafter the manner or the on test, produced about arm-no oi the invention 4,0 prepared the mixture was formed- This about octane (C. 1". D equal vo of distillate fuel, and o! the order of 10% by weight of gas. The coke deposit was only about 3.6% by weight oi the charge.

From this example it is evident that catalysts produce only small quantities of coky deposit evenwhen utilized to promote cracking or heavy charging stocks which tend to decompose readily into products which are coky' in nature. The gasolines produced possessed the iowacid heat and low gum content and other properties characteristic oi the highly stable gasoiines produced according to the invention.

Also, the catalysts o! the invention tend to produce only small quantities of coke when more refractory hydrocarbon fractions are cracked or reformed in their presence. I Thus, a catalyst produced by calcination of a composite tree or alkali metal prepared from the reactants and under the conditions-set forth for the-third catalyst of this example promoted volume of a gasoline having octane rating or about 80 (C. F. R. motor method) together with only about 3.5% of coke naphtha charge having 136 F., an octane rating an aniline point oi about of about 33.5 (C. F. R.

motormethod) and a boiling range or about 420* A catalyst consisting of the substantially pure nucleus or a silica-alumina-zirconia zeolite was irom the solutions prepared as follows.

1. 57.5 parts by weight of commercial sodium silicate as described in Example 2 were diluted with about 45.5 parts of water.

2. About 3 parts of solidsodium aluminate such as described in Example 2 were diluted with about 63 parts of water.

3. About 5 parts by weight or ZrOCh and about 11 parts of NHACI were dissolved in about 42 parts or water.

Solutions 1 and 2 are mixed to form a sol into a stream of which solution 3 was injected. Practically a gel having pH of about 9.2 and embracing ractically all the constituents or gel, in unwashed condition, was dried at about 200 F. anci water .washed until substantially free of water soluble solution of NH4C1 until Then, after base exchanged with a substantially free 01 sodium oxide.

calcination at about 1400 F. for a period orabout 10 hours in a stream or air containing 5% A: and 9% ZrOz and'ot the order of 0.08% Nil-2O, was utilized to promote cracking oi the gas oil described in Example 1 under substantially the vsame conditions. The gasoline produced which had an octane rating or about 80 (C. F. R. motor method) and acid heat 01 about 36 F. amounted to about 45.5% by volone 01 the gas 01 the gas oil charge. An approximately equal volume or light gas oil having a boiling range approximating that oi the charge was produced together with about 2.9% by weight 01 coke and 5.4% by weight of gas. a

motor met han.

production or about 54% by by weight, from a heavy its sodium replaced practically 'perature of the order of 200' mint: 4 v l A silica-alumina-seolite with substantially all by ammonium was prepared inthe following manner: a I

About 106 parts by weight of commercial sodium silicate solution such as described in Exampie 2 was diluted with about 47 parts of water andmixedwithasolutiouofapartsofsodium aluminate dissolvedinflilpartsofwaterto form -asolwhichwsseosgulatedbymixinginabout 2'1 parts of ammonium sulphate disolved in about 83 parts of water. The gel which formed immediately. after drying at tem- 1'. and wishing to substantial freedom of soluble salts. was baseetchanged with a solution of ammonium phate until substantially freeof sodium Glide.-

About 1 part'by weight of the resulting ammonium containing zeolite in the form of grantionofozpartbyweishtofzrociesnsodissolvediniparts otwater. 'I'hegranulesthen werewashedwithwateranddriedataboutmm it, whereupon then were calcined for about 10 hours at temperature of approximately 1400' F.

gasoildescribedinltxamplelundersubstanproducedahouteim by volumeofgasolineofabout 'lfloctaneic. 1112..

States Patent No. 2,146,718 to R. Bond, Jn, dated February 14, 1989, which reissued as Patent No. Rs 21,690 on January 14, i941.

, The high anti-knock rating. stability and other valuable properties of vention are probably due to the fact that the selective catalysts promotes formation of'stable branchchainparailinstotheexclusimorsubstantially so, of reactions which terminate with the formation of olefins or which convert straight chain prepouderating. as or higher than 4:1 over the straight chain compounds; in fact, their content of branch ules was immersed for abiiitranhourina 801M) whichhas heat exchange medium. for

'cycleso chain pars-mos usually exceeds their content of any other type of. hydrocarbons. y

when the charging stock contains refractory sulphur components. such components are converted into easily removable form, the resulting stable motor fuel often being capable of meeting market specifications for sulphur content and of passing accepted corrosion tests without befurther purification, except posing subiected to sibly a suitable treatment to remove traces of hydrogen sulphide, for example. a light caustic wash. In addition. when the charge subjected to the selective a naphtha, the resulting product having low acid heat and improved octane rating is more respective such as tetraethyl lead.

in order to provide continuous flow of react-- ants to and of reaction products from a plant a plurality of converters is preferably employed. each utilized alternately on stream and in regeneration and operated in coordination or in that the stream of reactants may be ormed from one converter at the end of an operating period therein to reactants. 'i'hepresentapplicstionisiupsrtacontinuation of my copending application Serial No. 310,762, filed December 23,- 1939.

Iclaimasmyinvention: ,LProceesofproducingIasoIinefromhydrocomprisproducts of the insplitting action of the catalyst is than the charge to addition agents during either or both of the onflied March 14,

conia prepared by calcination of a composite prepared by interaction of a sol containing silica,

alumina and alkali metal, a zirconium compound, and a compound containing an anion ofa non-atmospheric element in amount equivalent to at least 0.2 the-total alkali metal oxide content of the sol, and removing alkali metal from the resulting composite of silica. alumina and sirconia by drying to the dried gel state and then base exchanging with a volatile or heat-unstable cation. I 2. Process of producing gasoline from ordinarily liquid hydrocarbon fractions comprising cracking such fractions in the presence of a catalyst prepared by calcination at temperature of at least 700' F. of a composite of silica. alumina and zirconia obtained by subjecting a seolite to mild treatment with acid and freeing the same of alkali metal, said zeolite having Patent No. 2,375,756.

Jill!!! n1. Ems,

been obtained by the dryingof a mixture of hydrous oxides and alkali metal cation.

3. Process according to claim 2 further characterized in that the acid treatment is eilected- .with an acid-reacting solution which simultaneously deposits hydrous zirconia on the zeolite.

4. The process of effecting hydrocarbon conversion reactions which comprises contacting a normally liquid hydrocarbon fraction under vapor phase cracking conditions with a calcined composite produced by the drying of a mixture of the hydrous oxides of silica, alumina and zirconia containing alkali metal whereby upon drying a base exchange composite is produced, and by base exchangi g alkali metal in ,said dried mixture for a volatile cation, and by calcination of the dried base exchangedbody.

JOHN R. BATES.

crn'rmcus or commoner.

It is-hereby certified that error appears in the printed specification of" the above mnbered patent requiring ccrrectipn "r0115": Page 1, second column, line hit, for 'hydrogels of" read --lqdroge1s or -3 page 5', first column, line 29, for "and point"- read --end pointline 56., for

t "C. 3.1!." read -'C. F. Rt"; page 6,,

first cohnsn, line 21, for

line 51, for "octairie" read "octane";

"catalysts" read --cata1ysis--;

and second column, line 7 for line 33, for "respective" read --responsive"; line 5;, tor '1918' rea'd "1939; line 63, ior 'A1ternativei1y" read --A1;terna'tive1 --'3 page 7 first column, line 5, for 'non-atalos meric" read -non-anphoteric-.-

and that the said Letters Patent should be read with this correction therein that the same m cantons to flie record of the ca se in the Patent Office.

Signed and sealed this flat of August, A. D. 1 .5.'

(seal) Leslie Fraz er First Assistant Gdnsissioner of Patents.

conia prepared by calcination of a composite prepared by interaction of a sol containing silica,

alumina and alkali metal, a zirconium compound, and a compound containing an anion ofa non-atmospheric element in amount equivalent to at least 0.2 the-total alkali metal oxide content of the sol, and removing alkali metal from the resulting composite of silica. alumina and sirconia by drying to the dried gel state and then base exchanging with a volatile or heat-unstable cation. I 2. Process of producing gasoline from ordinarily liquid hydrocarbon fractions comprising cracking such fractions in the presence of a catalyst prepared by calcination at temperature of at least 700' F. of a composite of silica. alumina and zirconia obtained by subjecting a seolite to mild treatment with acid and freeing the same of alkali metal, said zeolite having Patent No. 2,375,756.

Jill!!! n1. Ems,

been obtained by the dryingof a mixture of hydrous oxides and alkali metal cation.

3. Process according to claim 2 further characterized in that the acid treatment is eilected- .with an acid-reacting solution which simultaneously deposits hydrous zirconia on the zeolite.

4. The process of effecting hydrocarbon conversion reactions which comprises contacting a normally liquid hydrocarbon fraction under vapor phase cracking conditions with a calcined composite produced by the drying of a mixture of the hydrous oxides of silica, alumina and zirconia containing alkali metal whereby upon drying a base exchange composite is produced, and by base exchangi g alkali metal in ,said dried mixture for a volatile cation, and by calcination of the dried base exchangedbody.

JOHN R. BATES.

crn'rmcus or commoner.

It is-hereby certified that error appears in the printed specification of" the above mnbered patent requiring ccrrectipn "r0115": Page 1, second column, line hit, for 'hydrogels of" read --lqdroge1s or -3 page 5', first column, line 29, for "and point"- read --end pointline 56., for

t "C. 3.1!." read -'C. F. Rt"; page 6,,

first cohnsn, line 21, for

line 51, for "octairie" read "octane";

"catalysts" read --cata1ysis--;

and second column, line 7 for line 33, for "respective" read --responsive"; line 5;, tor '1918' rea'd "1939; line 63, ior 'A1ternativei1y" read --A1;terna'tive1 --'3 page 7 first column, line 5, for 'non-atalos meric" read -non-anphoteric-.-

and that the said Letters Patent should be read with this correction therein that the same m cantons to flie record of the ca se in the Patent Office.

Signed and sealed this flat of August, A. D. 1 .5.'

(seal) Leslie Fraz er First Assistant Gdnsissioner of Patents. 

